Preparation method of diaryl carbazole-based material

Abstract

The invention discloses a preparation method of a diaryl carbazole-based material, and relates to the technical field of organic light-emitting devices. The method comprises the following steps: carrying out nitration reaction on 4-bromo-2-chloro-1-fluorobenzene to obtain an intermediate A; carrying out Suzuki coupling reaction on the intermediate A and 1-naphthaleneboronic acid to obtain a coupling intermediate B; carrying out nitro ring closing reaction on the intermediate B to prepare an intermediate C; coupling the intermediate C with iodobenzene or an iodobenzene derivative D to synthesize an intermediate E; preparing a boronic acid pinacol ester intermediate F from the intermediate E; carrying out Suzuki coupling reaction on the intermediate F and o-bromoaniline or an o-bromoaniline derivative G to obtain an intermediate H; performing ring closing on the intermediate H under an alkaline condition to obtain an intermediate I; and carrying out coupling reaction on the intermediate I and a halogenated aryl derivative J to obtain the diaryl carbazole material. The preparation route provided by the invention is high in reaction selectivity, single in product and free of obvious reaction defects, and the problems of ring closing reaction isomers and bromination reaction polybromination do not exist.

Description

Technical Field

[0001] The invention relates to the technical field of organic light-emitting devices, and in particular to a preparation method based on diarylcarbazole materials. Background Art

[0002] Organic Light-Emitting Diode (OLED) has many advantages such as unique high resolution, wide viewing angle, full-color display, bendability, foldability, ultra-thinness and lightness. It is widely used in information display, solid-state lighting, sensing and other fields, and has huge market prospects.

[0003] Luminescent materials are the core of OLED technology. Luminescent materials are generally composed of host-guest doping. The host material transmits charges and generates excitons, while the guest molecules capture excitons to achieve luminescence. With the popularization of OLED technology, higher requirements are also put forward for the luminescent performance and self-strength of materials. For example, large-size TVs and car displays require materials to have higher luminous efficiency and stability, and be able to adapt to sunlight, bumpy and other usage environments. However, current luminescent materials still have problems such as insufficient luminous efficiency, insufficient stability, and low glass transition temperature Tg. Therefore, it is urgent to develop luminescent materials with higher luminous efficiency and stability.

[0004] Diarylcarbazole materials are an important class of nitrogen-containing heterocyclic compounds. They are modified by introducing aromatic groups into the carbazole group, which enhances the rigid structure of the conjugated fused ring and facilitates the transmission of holes. They have a higher triplet energy level and better electron donation ability, and are ideal materials for the development of main materials. Their devices have the characteristics of low power consumption, long driving life and high luminous efficiency, with obvious structural advantages and great research value.

[0005] There are three methods for preparing diarylcarbazole materials in the prior art.

[0006] Method 1:

[0007]

[0008] Problems exist: (1) There are two ring-closing positions in the ring-closing reaction from L4 to L5, so 5 to 20% of ring-closing isomers will be produced, the reaction selectivity is poor, and material waste is caused; (2) The synthesis of L1, L3, L4, L5, and L6 all require the use of expensive catalysts, among which L4 to L5 requires 4% mol palladium acetate to achieve the ideal effect, which greatly increases the synthesis cost. For details, see WO2015099486A1.

[0009] Method 2:

[0010]

[0011] Problems: There are two ring-closing sites in the M3→M4 nitro ring-closing reaction, which can produce about 30% of ring-closing isomers, and the solubility of the target product M4 is better than that of the isomers, making purification extremely difficult. For details, see W02018021737A1. There is another similar method to make M2 into boronic acid, which has the same problems and is difficult to purify. For details, see CN202110915767.7.

[0012] Method 3:

[0013]

[0014] Problems exist: (1) Polybrominated impurities are easily generated on the naphthalene ring during the N2→N3 bromination reaction, which is not conducive to subsequent purification; (2) Since the N5→N6 ring-closure reaction is selective, in order to avoid isomerization, only para-substituted aniline can be selected, which greatly limits the expansion of diarylcarbazole materials. For details, see CN116535408A.

[0015] In summary, the prior art faces the problem of producing isomers when synthesizing diarylcarbazole materials: the isomers produced when preparing L5 from L4 in method 1 and when preparing M4 from M3 in method 2 need to be purified and removed, resulting in material waste; in order to avoid the production of isomers when preparing N6 from N5 in method 3, the research scope of derivatives is limited; at the same time, the above three methods repeatedly use a large amount of expensive palladium catalysts, resulting in high costs and being unfavorable for industrial production. Summary of the invention

[0016] In view of the deficiencies in the above-mentioned background technology, the present invention mainly solves the technical problem that the prior art has the problem of producing isomers and polybromination in the process of preparing diarylcarbazole materials. The present invention provides a preparation method based on diarylcarbazole materials. The preparation route provided by the present invention has high reaction selectivity, a single product, no obvious reaction defects, no problems of ring-closing reaction isomers and bromination reaction polybromination, and the purification yield of the last step of the derivative is 70-75%, and the yields of the remaining intermediates are all above 80%, which is better than the ring-closing reaction yield of 50-70% in the known route in terms of key steps.

[0017] The first object of the present invention is to provide a preparation method based on diaryl carbazole material, comprising the following steps: using 4-bromo-2-chloro-1-fluorobenzene to obtain intermediate A through nitration reaction; using intermediate A and 1-naphthaleneboric acid to obtain coupling intermediate B through Suzuki coupling reaction; using intermediate B to obtain intermediate C through nitro ring-closing reaction; synthesizing intermediate E from intermediate C with iodobenzene or iodobenzene derivative D; using intermediate E to prepare boronic acid pinacol ester intermediate F; using intermediate F and o-bromoaniline or o-bromoaniline derivative G through Suzuki coupling reaction to obtain intermediate H; closing the intermediate H under alkaline conditions to obtain intermediate I; coupling reaction of intermediate I and halogenated aryl derivative J to obtain diaryl carbazole material K;

[0018] The synthetic route is as follows:

[0019]

[0020] wherein R1-R3 are independently selected from hydrogen, deuterium, halogen, cyano, C1-C30 substituted or unsubstituted alkyl, C2-C30 substituted or unsubstituted alkenyl, C2-C30 substituted or unsubstituted alkynyl, C3-C30 substituted or unsubstituted cycloalkyl, C1-C30 substituted or unsubstituted alkoxy, C1-C30 substituted or unsubstituted silanyl, C6-C60 substituted or unsubstituted aryl, C3-C30 substituted or unsubstituted heteroaryl, or Ring A that shares one side with an adjacent phenyl group to form a condensed ring;

[0021] The ring A is selected from a benzene ring, a 3- to 7-membered saturated or partially unsaturated carbon ring, a 3- to 7-membered saturated or partially unsaturated hetero ring, a C6-C60 fused ring aromatic group, or a C3-C30 fused ring hetero aromatic group.

[0022] The second object of the present invention is to provide a diarylcarbazole-based material.

[0023] The third object of the present invention is to provide an application of a diarylcarbazole material in an organic light-emitting device.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] The invention provides a preparation method based on diarylcarbazole materials. The method has high reaction selectivity, single product, no obvious reaction defects, no problems of isomers in ring-closing reaction and polybromination in bromination reaction, a purification yield of 70-75% excluding the last step of derivatives, and yields of other intermediates are all above 80%, which is superior to the ring-closing reaction yield of 50-70% in the known route in terms of key steps.

[0026] In the preparation route provided by the present invention, intermediate H is prepared from intermediate F, and the most widely used Suzuki coupling method is adopted for connection. The raw material bromo derivative is easy to obtain, which enriches the range of selection of modified fragments and greatly expands the development field of diarylcarbazole materials.

[0027] In the preparation route provided by the present invention, intermediate I is prepared from intermediate H, fluorobenzene and aniline are used for ring closure under alkaline conditions of potassium tert-butoxide, no catalyst is needed, raw materials are cheap and easily available, and compared with the chlorine ring closure used in route one and the bromine ring closure used in route three, both of which require the use of 2-4% palladium acetate catalysis (unit price of palladium acetate: 240 yuan / g), the production cost is greatly saved, and the method has a significant advantage. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is the H-NMR diagram of Synthesis Example K-3 of the present invention;

[0029] Figure 2 A structural diagram of an organic electroluminescent device in an embodiment of the device of the present invention;

[0030] Among them, 1-substrate; 2-anode; 3-hole injection layer; 4-hole transport layer; 5-light-emitting layer; 6-electron transport layer; 7-electron injection layer; 8-cathode. DETAILED DESCRIPTION

[0031] In order to enable those skilled in the art to better understand and implement the technical solution of the present invention, the present invention is further described below in conjunction with specific embodiments and drawings, but the embodiments are not intended to limit the present invention.

[0032] The purpose of the present invention is to provide a diarylcarbazole material, and to solve the problems of isomers and polybromination in the process of preparing the diarylcarbazole material, to provide a new preparation method, and to expand the research scope of the diarylcarbazole material.

[0033] The first aspect of the present invention provides a method for preparing a diarylcarbazole material, comprising the following steps:

[0034] 4-bromo-2-chloro-1-fluorobenzene is used to obtain intermediate A through nitration reaction;

[0035] Intermediate A and 1-naphthaleneboronic acid are used to obtain coupling intermediate B through Suzuki coupling reaction;

[0036] Intermediate C is prepared by using intermediate B through nitro ring-closing reaction;

[0037] Intermediate C is used with iodobenzene or iodobenzene derivative D to synthesize intermediate E;

[0038] Intermediate E is used to prepare the boric acid pinacol ester intermediate F;

[0039] Intermediate F and o-bromoaniline or o-bromoaniline derivative G are subjected to Suzuki coupling reaction to obtain intermediate H;

[0040] The intermediate H is cyclized under alkaline conditions to obtain the intermediate I;

[0041] The intermediate I and the halogenated aryl derivative J are coupled to obtain the diaryl carbazole material K;

[0042] The synthetic route is as follows:

[0043]

[0044] wherein R1-R3 are independently selected from hydrogen, deuterium, halogen, cyano, C1-C30 substituted or unsubstituted alkyl, C2-C30 substituted or unsubstituted alkenyl, C2-C30 substituted or unsubstituted alkynyl, C3-C30 substituted or unsubstituted cycloalkyl, C1-C30 substituted or unsubstituted alkoxy, C1-C30 substituted or unsubstituted silanyl, C6-C60 substituted or unsubstituted aryl, C3-C30 substituted or unsubstituted heteroaryl, or Ring A that shares one side with an adjacent phenyl group to form a condensed ring;

[0045] The ring A is selected from a benzene ring, a 3- to 7-membered saturated or partially unsaturated carbon ring, a 3- to 7-membered saturated or partially unsaturated hetero ring, a C6-C60 fused ring aromatic group, or a C3-C30 fused ring hetero aromatic group.

[0046] The invention adopts 4-bromo-2-chloro-1-fluorobenzene as a starting material for nitration reaction in the first step. Due to the positioning effect of the bromine atom and the para-position occupation of the fluorine atom, the electrophilic reaction can only occur at the ortho position of the bromine atom, and the product is single; the second step is coupled to the 1-position of the naphthalene ring. Since the formed five-membered ring structure is more stable, the position of the nitro ring closure in the third step has high selectivity; the fourth step introduces a phenyl group to avoid the influence of the carbazole structure on the subsequent reaction; the fifth step is to prepare boric acid ester by using a palladium catalytic reaction of the bromide; the sixth step is to select an ortho-bromoarylamine for coupling reaction, so that the ring closure reaction in the seventh step has a unique structure, and the generation of isomers due to the existence of two ring closure positions is avoided; at the same time, since the chlorine atom is locked in advance at the starting material stage, the problem of multiple bromination of bromine in the later stage is avoided.

[0047] The iodobenzene or iodobenzene derivative D comprises the following structure:

[0048]

[0049] The o-bromoaniline or o-bromoaniline derivative G comprises one of the following structures:

[0050]

[0051] The halogenated aryl derivative J comprises one of the following structures:

[0052]

[0053] The intermediate A is prepared according to the following steps: add dichloromethane, concentrated sulfuric acid and 4-bromo-2-chloro-1-fluorobenzene to the reactor in sequence, start stirring, introduce nitrogen, add 68% concentrated nitric acid dropwise at 0°C, heat to reflux for 1-2h, cool to 25±5°C, separate the lower acid solution, wash the organic phase with water, wash with sodium bicarbonate solution, wash with water and then concentrate, add n-hexane, heat to reflux for 1-2h, cool to 0±5°C, crystallize for 1-2h, filter, and dry to obtain the intermediate A;

[0054] The intermediate B is prepared according to the following steps: add intermediate A, 1-naphthaleneboric acid, potassium carbonate, toluene, ethanol, and pure water into a reactor, start stirring, introduce nitrogen, add tetrakis(triphenylphosphine)palladium, heat to 75±5°C for reaction for 3-6h, cool to 35±5°C, separate the water layer and wash with water, keep at 60±5°C and pass through a silica gel column, concentrate at normal pressure, add ethanol and heat to reflux for 1-2h, cool to 25±5°C, filter, and dry to obtain intermediate B;

[0055] The intermediate C is prepared according to the following steps: adding intermediate B, triphenylphosphine and o-dichlorobenzene into a reactor, starting stirring, introducing nitrogen, heating to 160±10°C for reaction for 8-12h, cooling to 90±5°C, distilling off o-dichlorobenzene under reduced pressure, cooling to 70±5°C, adding ethanol, reflux beating for 1-2h, cooling to 25±5°C, filtering, reflux beating the filter cake with n-hexane for 1-2h, cooling to 25±5°C, filtering, and drying to obtain intermediate C.

[0056] The intermediate E is prepared according to the following steps: adding intermediate C, iodobenzene derivative D, cuprous iodide, 1,10-phenanthroline, potassium carbonate, and dioxane into a reactor, stirring, introducing nitrogen, heating to reflux and keeping the temperature for reaction for 8 to 12 hours, cooling to 50±5°C, filtering, rinsing the filter cake with dioxane, concentrating and evaporating to remove the dioxane, adding toluene and water to extract and separate the phases, concentrating the toluene phase at normal pressure, adding ethanol, heating to reflux and beating for 1 to 2 hours, cooling to 25±5°C, filtering, and drying to obtain the intermediate E;

[0057] The intermediate F is prepared according to the following steps: adding intermediate E, pinacol borate, tri(benzylideneacetone) dipalladium, X-Phos, potassium acetate and dioxane into a reactor, starting stirring, introducing nitrogen, heating the materials to reflux reaction for 6 to 8 hours, cooling to 50±5°C, filtering, rinsing the filter cake with dioxane, concentrating and evaporating to remove dioxane, adding dichloromethane and water to extract and separate the phases, concentrating the dichloromethane phase at normal pressure, adding n-hexane, heating to reflux and beating for 1 to 2 hours, then cooling to 25±5°C, filtering, and drying to obtain intermediate F.

[0058] The intermediate H is prepared according to the following steps: adding intermediate F, o-bromoaniline or o-bromoaniline derivative G, potassium carbonate, toluene and pure water into a reactor, starting stirring, adding bistriphenylphosphine palladium dichloride under nitrogen protection, heating to reflux reaction for 2 to 4 hours, cooling to 50±5°C, standing to separate the water layer, washing the organic phase with water, keeping the temperature at 60±5°C to pass through a silica gel column and eluting the silica gel, combining the organic layers, distilling toluene at normal pressure, adding ethanol to reflux and slurry for 1 to 2 hours, cooling to 25±5°C, filtering to obtain an off-white intermediate H;

[0059] The intermediate I is prepared according to the following steps: adding intermediate H, potassium tert-butoxide and dimethyl sulfoxide to a reactor, starting stirring, introducing nitrogen, heating the material to 90±5°C for 2-4h, cooling to 25±5°C, adding water to separate the material, stirring for 0.5-1h, filtering, and washing the filter cake with water; transferring the filter cake to a reactor, adding chlorobenzene, heating to dissolve the material, keeping the temperature at 120±5°C, passing through a silica gel column, concentrating at normal pressure, cooling to 25±5°C, keeping the temperature for 1-2h, filtering, and obtaining intermediate I;

[0060] The diarylcarbazole material K is prepared according to the following steps: adding intermediate I, halogenated aryl derivative J, sodium tert-butoxide and toluene into a reactor, starting stirring, introducing nitrogen, and when the material temperature rises to 60±5°C, adding 10% tri-tert-butylphosphine toluene solution and tri(benzylideneacetone)dipalladium, and then heating to reflux for reaction for 1-2h, cooling to 50±5°C after the reaction, adding water to quench the reaction, separating water, washing the organic phase with water once, keeping the temperature at 80±5°C to pass through a silica gel column and eluting the silica gel, combining the filtrate, concentrating and evaporating toluene, cooling to 70±5°C, adding ethanol, cooling to 25±5°C, filtering to obtain an off-white solid, and then recrystallizing through toluene / ethyl acetate for 2-3 times to obtain an off-white solid diarylcarbazole material K.

[0061] The Pd catalyst is palladium acetate, tris(dibenzylideneacetone)dipalladium, tetrakistriphenylphosphine palladium, [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium dichloromethane complex or bis(triphenylphosphine)palladium dichloride.

[0062] The second aspect of the present invention provides a diarylcarbazole-based material, wherein the general structural formula of the diarylcarbazole-based material is shown in the following formula (K):

[0063]

[0064] In formula (K), R1 to R3 are independently selected from hydrogen, deuterium, halogen, cyano, C1-C30 substituted or unsubstituted alkyl, C2-C30 substituted or unsubstituted alkenyl, C2-C30 substituted or unsubstituted alkynyl, C3-C30 substituted or unsubstituted cycloalkyl, C1-C30 substituted or unsubstituted alkoxy, C1-C30 substituted or unsubstituted silanyl, C6-C60 substituted or unsubstituted aryl, C3-C30 substituted or unsubstituted heteroaryl, or a ring A that shares one side with an adjacent phenyl group to form a condensed ring; the substituents include substituted C1-C60 The substituents in the alkyl group, substituted C3-C60 cycloalkyl group, substituted C1-C60 heteroalkyl group, substituted C6-C60 aryl group, substituted C3-C60 heteroaryl group, substituted C6-C30 arylene group, substituted C6-C30 heteroarylene group, substituted C6-C60 arylamine group and substituted C3-C60 heteroarylamine group are selected from one or a combination of at least two of deuterium, halogen, cyano, C1-C12 alkyl group, C3-C60 cycloalkyl group, C6-C60 aryl group, C3-C60 heteroaryl group, C6-C60 arylamine group and C3-C60 heteroarylamine group.

[0065] The ring A is selected from a benzene ring, a 3- to 7-membered saturated or partially unsaturated carbon ring, a 3- to 7-membered saturated or partially unsaturated hetero ring, a C6-C60 fused ring aromatic group, or a C3-C30 fused ring hetero aromatic group.

[0066] The diarylcarbazole-based material includes any one of the following compounds:

[0067]

[0068]

[0069] The third aspect of the present invention provides an application of a diarylcarbazole material in an organic light-emitting material.

[0070] It should be noted that the experimental methods used in the present invention are all conventional methods unless otherwise specified; the reagents and materials used are all commercially available unless otherwise specified.

[0071] Example 1

[0072] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-1:

[0073]

[0074] The synthesis route of the diarylcarbazole material shown in K-1 is as follows:

[0075]

[0076] Synthesis A: Add 300mL of dichloromethane, 120g of concentrated sulfuric acid and 4-bromo-2-chloro-1-fluorobenzene (60g, 0.286mol, 1eq) to a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, start stirring, introduce nitrogen, and add 68% concentrated nitric acid (26.5g, 0.286mol, 1eq) dropwise at 0°C. The reaction is exothermic, and the temperature is controlled to <15°C during the addition process. After the addition is completed, the temperature is raised to reflux, and the reaction is continued for 2h. The reaction of the raw material 4-bromo-2-chloro-1-fluorobenzene is monitored to be complete. After HPLC is qualified, stand and separate, separate the lower sulfuric acid layer, and wash the dichloromethane phase with 100mL of water, 100mL of saturated sodium bicarbonate aqueous solution, and 100mL of water. The dichloromethane was evaporated after concentration, and 90 mL of n-hexane was added. The temperature was raised to reflux for 1 h, and then the temperature was lowered to 0°C for crystallization for 2 h. The mixture was filtered, rinsed with an appropriate amount of n-hexane, and dried to obtain 60.8 g of a yellow-green solid with a purity of 98.4% and a yield of 83.5%.

[0077] Synthesis B: Add 300mL toluene, 150mL pure water, potassium carbonate (66g, 0.477mol, 2.0eq), 1-naphthaleneboronic acid (49.2g, 0.286mol, 1.2eq), intermediate A (60.8g, 0.239mol, 1.0eq) and 50mL ethanol to a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser to rinse the bottle wall. Start stirring, add tetrakis(triphenylphosphine)palladium (2.8g, 0.0024mol, 0.01eq) under continuous N2 protection, and then heat to reflux for 3h. HPLC monitors the complete reaction of intermediate A. After HPLC is qualified, stand and separate the water layer, wash the organic phase with 200mL water once, keep warm at 60℃ and pass through a 5cm thick silica gel column, and rinse the silica gel with an appropriate amount of toluene. The organic layers were combined, and toluene was evaporated at normal pressure until a yellow-green solid precipitated. Then 150 mL of ethanol was added and refluxed for 1 h. The mixture was cooled to room temperature and filtered to obtain 64.7 g of a yellow-green solid with a purity of 99.2% and a yield of 90%.

[0078] Synthesis C: Into a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate B (64.7g, 0.215mol, 1.0eq), triphenylphosphine (169g, 0.644mol, 3.0eq) and 500mL o-dichlorobenzene were charged, stirring was started, nitrogen was continuously introduced, the material was heated to reflux reaction for 12h, and HPLC monitored that the intermediate B was basically reacted completely. After HPLC was qualified, the material was cooled to 90°C, o-dichlorobenzene was evaporated under reduced pressure, cooled to 70°C, 500mL ethanol was added to reflux and beat for 1h, cooled to room temperature, filtered, and the filter cake was added with 300mL n-hexane to reflux and beat for 1h, cooled to room temperature, filtered, and dried to obtain 47.5g of light brown solid, purity 97.6%, yield 82%.

[0079] Synthesis of E-1: To a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate C (47.5 g, 0.176 mol, 1.0 eq), iodobenzene D-1 (54 g, 0.264 mol, 1.5 eq), cuprous iodide (3.4 g, 0.0176 mol, 0.1 eq), 1,10-phenanthroline (3.2 g, 0.0176 mol, 0.1 eq), potassium carbonate (48.6 g, 0.352 mol, 2.0 eq) and 450 mL of dioxane were added. Stirring was started, nitrogen was continuously introduced, the material was heated to reflux, and the reaction was kept warm for 9 h. The reaction of intermediate C was completed under HPLC monitoring. The mixture was cooled to 50°C and filtered. The filter cake was rinsed with 100 mL of dioxane and concentrated to remove the dioxane. 400 mL of toluene and 200 mL of water were added to extract and separate the phases. The toluene phase was concentrated under normal pressure, 300 mL of ethanol was added, the temperature was raised to reflux and slurrying for 1 h, and then the temperature was lowered to 25°C, filtered, and dried to obtain 51.2 g of an off-white solid with a purity of 98.4% and a yield of 84%.

[0080] Synthesis of F-1: To a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, add intermediate E-1 (51.2 g, 0.148 mol, 1.0 eq), pinacol diboron (41.4 g, 0.163 mol, 1.1 eq), tri(benzylideneacetone)dipalladium (1.4 g, 0.0015 mol, 0.01 eq), X-Phos (2.1 g, 0.0044 mol, 0.03 eq), potassium acetate (28.4 g, 0.296 mol, 2.0 eq), 450 mL of dioxane, start stirring, introduce nitrogen, heat the material to reflux, and react for 6 h. The reaction of intermediate E-1 is completed under HPLC monitoring. The mixture was cooled to 50°C and filtered. The filter cake was rinsed with 100 mL of dioxane and concentrated to remove the dioxane. 400 mL of dichloromethane and 200 mL of water were added to extract the phases. The dichloromethane organic phase was concentrated under normal pressure. 300 mL of n-hexane was added. The mixture was heated to reflux and slurried for 1 h. The mixture was cooled to 25°C and filtered and dried to obtain 55.1 g of an off-white solid with a HPLC purity of 98.8% and a yield of 85.1%.

[0081] Synthesis of H-1: Add intermediate F-1 (55.1 g, 0.126 mol, 1.0 eq), o-bromoaniline G-1 (22.8 g, 0.132 mol, 1.05 eq), potassium carbonate (34.8 g, 0.252 mol, 2.0 eq), 400 mL toluene and 150 mL pure water to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, add bistriphenylphosphine palladium dichloride (0.9 g, 0.0013 mol, 0.01 eq) under continuous nitrogen protection, and then heat to reflux for 3 h. HPLC monitors the complete reaction of intermediate F-1. After HPLC is qualified, cool to 50 ° C, stand to separate the water layer, wash the organic phase with 100 mL of water once, keep warm at 60 ° C and pass through a 5 cm thick silica gel column and rinse the silica gel with an appropriate amount of toluene. The organic layers were combined, toluene was evaporated at normal pressure, and then 150 mL of ethanol was added to reflux and slurry for 1 h. The temperature was lowered to 25° C. and filtered to obtain 43.6 g of an off-white solid with a purity of 98.2% and a yield of 86%.

[0082] Synthesis of I-1: Add intermediate H-1 (43.6 g, 0.108 mol, 1.0 eq), potassium tert-butoxide (24.3 g, 0.216 mol, 2.0 eq) and 100 mL of dimethyl sulfoxide to a 500 mL reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, start stirring, and introduce nitrogen. The material is heated to 90 ° C and kept for 3 hours. HPLC monitors the complete reaction of intermediate H-1. After HPLC is qualified, cool to room temperature, add 250 mL of water, stir for 0.5 hours, filter, and rinse the filter cake with water. The filter cake is transferred to a bottle, 300 mL of chlorobenzene is added to heat and evaporate the water-soluble material, keep warm at 130 ° C and pass through a 5 cm thick silica gel column, then concentrate to 100 mL, cool to 25 ° C for crystallization for 1 hour, filter, and obtain 33.5 g of off-white solid with a purity of 99.4% and a yield of 81%.

[0083] Synthesis of K-1: Into a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-1 (33.5 g, 0.088 mol, 1.0 eq), bromobenzene J-1 (20.7 g, 0.132 mol, 1.5 eq), sodium tert-butoxide (12.6 g, 0.132 mol, 1.5 eq) and 500 mL of toluene were placed, stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (7.1 g, 0.0035 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the temperature was raised to reflux for reaction for 2 h. Samples were taken and HPLC was used to monitor the completion of the reaction of intermediate I-1. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the temperature was kept at 80°C and passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to evaporate toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and filtered to obtain an off-white solid wet product, which was then recrystallized twice from toluene / ethyl acetate to obtain 30 g of an off-white solid with a purity of 99.93% and a yield of 75%.

[0084] Example 2

[0085] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-2:

[0086]

[0087] The preparation steps of the diarylcarbazole material K-2 shown in the embodiment 1 are different from the preparation steps of the diarylcarbazole material K-1 provided in the embodiment 1 only in that:

[0088] The compound represented by formula J-2 is used to replace compound J-1 in step 8 of Example 1. The synthetic route of K-2 is as follows:

[0089]

[0090] Synthesis of K-2: Into a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-1 (33.5 g, 0.088 mol, 1.0 eq), p-bromobiphenyl J-2 (22.6 g, 0.097 mol, 1.1 eq), sodium tert-butoxide (12.6 g, 0.132 mol, 1.5 eq) and 500 mL of toluene were placed, stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (7.1 g, 0.0035 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the temperature was raised to reflux for reaction for 2 h. Samples were taken and HPLC was used to monitor the completion of the reaction of intermediate I-1. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the mixture was kept at 80°C and passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to remove toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and an off-white solid was obtained by filtration. The off-white solid was recrystallized twice from toluene / ethyl acetate to obtain 33.8 g of an off-white solid with a purity of 99.93% and a yield of 72%.

[0091] Example 3

[0092] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-3:

[0093]

[0094] The synthesis route of the diarylcarbazole material shown in K-3 is as follows:

[0095]

[0096] The difference between the preparation steps of K-3 and the preparation steps of the diarylcarbazole material shown in K-1 provided in Example 1 is only that:

[0097] The compound represented by formula J-3 is used instead of compound J-1 in step 8 of Example 1.

[0098] Synthesis of K-3: Into a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-1 (33.5 g, 0.088 mol, 1.0 eq), 4-bromophenyldibenzofuran J-3 (31.4 g, 0.097 mol, 1.1 eq), sodium tert-butoxide (12.6 g, 0.132 mol, 1.5 eq) and 500 mL of toluene were placed, stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (7.1 g, 0.0035 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the temperature was raised to reflux for reaction for 2 h, and sampling was performed to monitor the completion of the reaction of intermediate I-1 by HPLC. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the temperature was kept at 80°C, passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to evaporate toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and an off-white solid was obtained by filtration. The off-white solid was recrystallized twice from toluene / ethyl acetate to obtain 40.7 g of an off-white solid with a purity of 99.91% and a yield of 74%.

[0099] See also Figure 1 Shown is the H-NMR spectrum of K-3.

[0100] Example 4

[0101] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-4:

[0102]

[0103] The synthesis route of the diarylcarbazole material shown in K-4 is as follows:

[0104]

[0105] The difference between the preparation steps of K-4 and the preparation steps of the diarylcarbazole material shown in K-1 provided in Example 1 is only that:

[0106] The compound represented by formula J-4 is used instead of compound J-1 in step 8 of Example 1.

[0107] Synthesis of K-4: Into a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-1 (33.5 g, 0.088 mol, 1.0 eq), 3-bromophenyldibenzofuran J-4 (31.4 g, 0.097 mol, 1.1 eq), sodium tert-butoxide (12.6 g, 0.132 mol, 1.5 eq) and 500 mL of toluene were placed, stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (7.1 g, 0.0035 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the temperature was raised to reflux for reaction for 2 h, and sampling was performed to monitor the completion of the reaction of intermediate I-1 by HPLC. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the mixture was kept at 80°C and passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to remove toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and an off-white solid was obtained by filtration. The off-white solid was recrystallized twice from toluene / ethyl acetate to obtain 39.6 g of an off-white solid with a purity of 99.93% and a yield of 72%.

[0108] Example 5

[0109] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-5:

[0110]

[0111] The synthesis route of the diarylcarbazole material shown in K-5 is as follows:

[0112]

[0113] The difference between the preparation steps of K-5 and the preparation steps of the diarylcarbazole material shown in K-1 provided in Example 1 is only that:

[0114] The compound represented by formula J-5 is used instead of compound J-1 in step 8 of Example 1.

[0115] Synthesis of K-5: Into a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-1 (33.5 g, 0.088 mol, 1.0 eq), p-bromophenylnaphthalene J-5 (27.5 g, 0.097 mol, 1.1 eq), sodium tert-butoxide (12.6 g, 0.132 mol, 1.5 eq) and 500 mL of toluene were placed, stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (7.1 g, 0.0035 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the temperature was raised to reflux for reaction for 2 h. Samples were taken and HPLC was used to monitor the completion of the reaction of intermediate I-1. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the temperature was kept at 80°C, passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to evaporate toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and an off-white solid was obtained by filtration. It was then recrystallized twice from toluene / ethyl acetate to obtain 38.6 g of an off-white solid with a purity of 99.90% and a yield of 75%.

[0116] Example 6

[0117] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-6:

[0118]

[0119] The synthesis route of the diarylcarbazole material shown in K-6 is as follows:

[0120]

[0121] Synthesis of E-6: Add intermediate C (47.5 g, 0.176 mol, 1.0 eq), 2-iodonaphthalene D-6 (49 g, 0.194 mol, 1.1 eq), cuprous iodide (3.4 g, 0.0176 mol, 0.1 eq), 1,10-phenanthroline (3.2 g, 0.0176 mol, 0.1 eq), potassium carbonate (48.6 g, 0.352 mol, 2.0 eq) and 450 mL of dioxane to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, continue to introduce nitrogen, heat the material to reflux, keep the temperature for 9 h, and monitor the complete reaction of intermediate C by HPLC. The mixture was cooled to 50°C and filtered. The filter cake was rinsed with 100 mL of dioxane and concentrated to remove the dioxane. 400 mL of toluene and 200 mL of water were added to extract and separate the phases. The toluene phase was concentrated under normal pressure, 300 mL of ethanol was added, the temperature was raised to reflux and slurrying for 1 h, the temperature was then reduced to 25°C, filtered, and dried to obtain 57.2 g of an off-white solid with a purity of 98.1% and a yield of 82%.

[0122] Synthesis of F-6: Add intermediate E-6 (57.2 g, 0.144 mol, 1.0 eq), bipyralidin (40.2 g, 0.158 mol, 1.1 eq), tri(benzylideneacetone)dipalladium (1.4 g, 0.0015 mol, 0.01 eq), X-Phos (2.1 g, 0.0044 mol, 0.03 eq), potassium acetate (27.6 g, 0.288 mol, 2.0 eq) and 450 mL of dioxane to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, introduce nitrogen, heat the material to reflux, and keep the temperature for 6 h. HPLC monitors the complete reaction of intermediate E-6. The mixture was cooled to 50°C and filtered. The filter cake was rinsed with 100 mL of dioxane and concentrated to remove the dioxane. 400 mL of dichloromethane and 200 mL of water were added to extract the phases. The dichloromethane organic phase was concentrated under normal pressure. 300 mL of n-hexane was added. The mixture was heated to reflux and slurried for 1 h. The mixture was cooled to 25°C and filtered and dried to obtain 58.8 g of an off-white solid with an HPLC purity of 98.2% and a yield of 84%.

[0123] Synthesis of H-6: Add intermediate F-6 (58.8 g, 0.121 mol, 1.0 eq), o-bromoaniline G-1 (21.8 g, 0.127 mol, 1.05 eq), potassium carbonate (33.4 g, 0.242 mol, 2.0 eq), 400 mL toluene and 150 mL pure water to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, add bistriphenylphosphine palladium dichloride (0.9 g, 0.0013 mol, 0.01 eq) under continuous nitrogen protection, and then heat to reflux for 3 h. HPLC monitors the complete reaction of intermediate F-6. After HPLC is qualified, cool to 50 ° C, stand to separate the water layer, wash the organic phase with 100 mL of water once, keep warm at 60 ° C and pass through a 5 cm thick silica gel column and rinse the silica gel with an appropriate amount of toluene. The organic layers were combined, toluene was evaporated at normal pressure, and then 150 mL of ethanol was added to reflux and slurry for 1 h. The temperature was lowered to 25° C. and filtered to obtain 45.4 g of an off-white solid with a purity of 98.6% and a yield of 83%.

[0124] Synthesis of I-6: Add intermediate H-6 (45.4g, 0.101mol, 1.0eq), potassium tert-butoxide (22.7g, 0.202mol, 2.0eq) and 100mL dimethyl sulfoxide to a 500mL reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, start stirring, and introduce nitrogen. The material is heated to 90°C for 3h of insulation reaction. HPLC monitors the complete reaction of intermediate H-6. After HPLC is qualified, cool to room temperature, add 250mL of water, stir for 0.5h, filter, and rinse the filter cake with water. The filter cake is transferred to a bottle, 300mL of chlorobenzene is added to heat and evaporate the water-soluble material, keep warm at 130°C and pass through a 5cm thick silica gel column, then concentrate to 100mL, cool to 25°C for crystallization for 1h, filter, and obtain 35.3g of off-white solid with a purity of 99.0% and a yield of 81%.

[0125] Synthesis of K-6: Into a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-6 (35.3 g, 0.082 mol, 1.0 eq), bromobenzene naphthalene J-5 (25.5 g, 0.091 mol, 1.1 eq), sodium tert-butoxide (11.8 g, 0.123 mol, 1.5 eq) and 500 mL toluene were placed. Stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (7.0 g, 0.0035 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the temperature was raised to reflux for reaction for 2 h, and sampling was performed to monitor the complete reaction of intermediate I-6 by HPLC. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the mixture was kept at 80°C and passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to remove toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and an off-white solid was obtained by filtration. The solid was recrystallized twice from toluene / ethyl acetate to obtain 37.5 g of an off-white solid with a purity of 99.92% and a yield of 72%.

[0126] Example 7

[0127] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-7:

[0128]

[0129] The synthesis route of the diarylcarbazole material shown in K-7 is as follows:

[0130]

[0131] Synthesis of E-7: To a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate C (47.5g, 0.176mol, 1.0eq), meta-iodobiphenyl D-7 (54.2g, 0.194mol, 1.1eq), cuprous iodide (3.4g, 0.0176mol, 0.1eq), 1,10-phenanthroline (3.2g, 0.0176mol, 0.1eq), potassium carbonate (48.6g, 0.352mol, 2.0eq) and 450mL of dioxane were added. Stirring was started, nitrogen was continuously introduced, the material was heated to reflux, and the reaction was kept warm for 9h. The reaction of intermediate C was monitored by HPLC. The mixture was cooled to 50°C and filtered. The filter cake was rinsed with 100 mL of dioxane and concentrated to remove the dioxane. 400 mL of toluene and 200 mL of water were added to extract and separate the phases. The toluene phase was concentrated under normal pressure. 300 mL of ethanol was added. The mixture was heated to reflux and slurried for 1 h. The mixture was cooled to 25°C, filtered, and dried to obtain 60.2 g of an off-white solid with a purity of 98.6% and a yield of 81%.

[0132] Synthesis of F-7: To a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, add intermediate E-7 (60.2g, 0.143mol, 1.0eq), pinacol diboron (40.2g, 0.158mol, 1.1eq), tri(benzylideneacetone)dipalladium (1.4g, 0.0015mol, 0.01eq), X-Phos (2.1g, 0.0044mol, 0.03eq), potassium acetate (27.6g, 0.288mol, 2.0eq), 450mL of dioxane, start stirring, introduce nitrogen, heat the material to reflux, and keep the reaction for 6h. HPLC monitors the completion of the reaction of intermediate E-7. The mixture was cooled to 50°C and filtered. The filter cake was rinsed with 100 mL of dioxane and concentrated to remove the dioxane. 400 mL of dichloromethane and 200 mL of water were added to extract the phases. The dichloromethane organic phase was concentrated under normal pressure. 300 mL of n-hexane was added. The mixture was heated to reflux and slurried for 1 h. The mixture was cooled to 25°C, filtered, and dried to obtain 60.2 g of an off-white solid with an HPLC purity of 98.3% and a yield of 82%.

[0133] Synthesis of H-7: Add intermediate F-7 (60.2 g, 0.117 mol, 1.0 eq), o-bromoaniline G-1 (21.1 g, 0.123 mol, 1.05 eq), potassium carbonate (32.3 g, 0.234 mol, 2.0 eq), 400 mL toluene and 150 mL pure water to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, add bistriphenylphosphine palladium dichloride (0.9 g, 0.0013 mol, 0.01 eq) under continuous nitrogen protection, and then heat to reflux for 3 h. HPLC monitors the complete reaction of intermediate F-7. After HPLC is qualified, cool to 50 ° C, stand to separate the water layer, wash the organic phase with 100 mL of water once, keep warm at 60 ° C and pass through a 5 cm thick silica gel column and rinse the silica gel with an appropriate amount of toluene. The organic layers were combined, toluene was evaporated at normal pressure, and then 150 mL of ethanol was added to reflux and slurry for 1 h. The temperature was lowered to 25° C. and filtered to obtain 44.2 g of an off-white solid with a purity of 97.8% and a yield of 79%.

[0134] Synthesis of I-7: Add intermediate H-7 (44.2g, 0.092mol, 1.0eq), potassium tert-butoxide (20.7g, 0.184mol, 2.0eq) and 100mL dimethyl sulfoxide to a 500mL reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, start stirring, pass nitrogen, heat the material to 90°C and keep the reaction for 3h, and monitor the complete reaction of intermediate H-7 by HPLC. After HPLC is qualified, cool to room temperature, add 250mL water, stir for 0.5h, filter, and rinse the filter cake with water. Transfer the filter cake to a bottle, add 300mL chlorobenzene and heat to evaporate the water-soluble material, keep 130°C and pass through a 5cm thick silica gel column, then concentrate to 100mL, cool to 25°C for crystallization for 1h, filter, and obtain 32.9g of off-white solid with a purity of 99.0% and a yield of 78%.

[0135] Synthesis of K-7: Into a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-7 (32.9 g, 0.072 mol, 1.0 eq), p-bromophenylnaphthalene J-5 (22.3 g, 0.079 mol, 1.1 eq), sodium tert-butoxide (10.4 g, 0.108 mol, 1.5 eq) and 500 mL toluene were placed. Stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (5.7 g, 0.003 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.66 g, 0.0007 mol, 0.01 eq) were added, and the temperature was raised to reflux for reaction for 2 h, and the reaction of intermediate I-7 was monitored by HPLC sampling. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the mixture was kept at 80°C and passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to remove toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and an off-white solid was obtained by filtration. The off-white solid was recrystallized twice from toluene / ethyl acetate to obtain 34.7 g of an off-white solid with a purity of 99.91% and a yield of 73%.

[0136] Example 8

[0137] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-8:

[0138]

[0139] The synthesis route of the diarylcarbazole material shown in K-8 is as follows:

[0140]

[0141] Synthesis of E-8: To a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, add intermediate C (47.5g, 0.176mol, 1.0eq), p-iodobiphenyl D-8 (54.2g, 0.194mol, 1.1eq), cuprous iodide (3.4g, 0.0176mol, 0.1eq), 1,10-phenanthroline (3.2g, 0.0176mol, 0.1eq), potassium carbonate (48.6g, 0.352mol, 2.0eq) and 450mL of dioxane, start stirring, continue to introduce nitrogen, heat the material to reflux, keep the reaction for 9h, and monitor the complete reaction of intermediate C by HPLC. The mixture was cooled to 50°C and filtered. The filter cake was rinsed with 100 mL of dioxane and concentrated to remove the dioxane. 400 mL of toluene and 200 mL of water were added to extract and separate the phases. The toluene phase was concentrated under normal pressure. 300 mL of ethanol was added. The mixture was heated to reflux and slurried for 1 h. The mixture was cooled to 25°C, filtered, and dried to obtain 60.7 g of an off-white solid with a purity of 98.6% and a yield of 82%.

[0142] Synthesis of F-8: To a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, add intermediate E-8 (60.7 g, 0.144 mol, 1.0 eq), pinacol diboron (40.2 g, 0.158 mol, 1.1 eq), tri(benzylideneacetone)dipalladium (1.4 g, 0.0015 mol, 0.01 eq), X-Phos (2.1 g, 0.0044 mol, 0.03 eq), potassium acetate (27.6 g, 0.288 mol, 2.0 eq), 450 mL of dioxane, start stirring, introduce nitrogen, heat the material to reflux, and keep the reaction for 6 h. The reaction of intermediate E-8 is completed under HPLC monitoring. The mixture was cooled to 50°C and filtered. The filter cake was rinsed with 100 mL of dioxane and concentrated to remove the dioxane. 400 mL of dichloromethane and 200 mL of water were added to extract the phases. The dichloromethane organic phase was concentrated under normal pressure. 300 mL of n-hexane was added. The mixture was heated to reflux and slurried for 1 h. The mixture was cooled to 25°C, filtered, and dried to obtain 59.3 g of an off-white solid with an HPLC purity of 97.8% and a yield of 80%.

[0143] Synthesis of H-8: Add intermediate F-8 (59.3 g, 0.115 mol, 1.0 eq), o-bromoaniline G-1 (20.8 g, 0.121 mol, 1.05 eq), potassium carbonate (31.8 g, 0.231 mol, 2.0 eq), 400 mL toluene and 150 mL pure water to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, add bistriphenylphosphine palladium dichloride (0.9 g, 0.0013 mol, 0.01 eq) under continuous nitrogen protection, and then heat to reflux for 3 h. HPLC monitors the complete reaction of intermediate F-8. After HPLC is qualified, cool to 50 ° C, stand to separate the water layer, wash the organic phase with 100 mL of water once, keep warm at 60 ° C and pass through a 5 cm thick silica gel column and rinse the silica gel with an appropriate amount of toluene. The organic layers were combined, toluene was evaporated at normal pressure, and then 150 mL of ethanol was added to reflux and slurry for 1 h. The temperature was lowered to 25° C. and filtered to obtain 44.7 g of an off-white solid with a purity of 98.2% and a yield of 81%.

[0144] Synthesis of I-8: Add intermediate H-8 (44.7 g, 0.093 mol, 1.0 eq), potassium tert-butoxide (20.7 g, 0.184 mol, 2.0 eq) and 100 mL of dimethyl sulfoxide to a 500 mL reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, start stirring, introduce nitrogen, heat the material to 90 ° C and keep the reaction for 3 h, and monitor the complete reaction of intermediate H-8 by HPLC. After HPLC is qualified, cool to room temperature, add 250 mL of water, stir for 0.5 h, filter, and rinse the filter cake with water. The filter cake is transferred to a bottle, 300 mL of chlorobenzene is added to heat and evaporate the water-soluble material, keep warm at 130 ° C and pass through a 5 cm thick silica gel column, then concentrate to 100 mL, cool to 25 ° C for crystallization for 1 h, filter, and obtain 33.6 g of off-white solid with a purity of 99.0% and a yield of 79%.

[0145] Synthesis of K-8: Into a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-8 (33.6 g, 0.073 mol, 1.0 eq), p-bromophenylnaphthalene J-5 (22.3 g, 0.079 mol, 1.1 eq), sodium tert-butoxide (10.4 g, 0.108 mol, 1.5 eq) and 500 mL toluene were placed. Stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (5.9 g, 0.003 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.66 g, 0.0007 mol, 0.01 eq) were added, and the temperature was raised to reflux for reaction for 2 h, and the reaction of intermediate I-8 was monitored by HPLC sampling. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the mixture was kept at 80°C and passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to remove toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and an off-white solid was obtained by filtration. The off-white solid was recrystallized twice from toluene / ethyl acetate to obtain 35.7 g of an off-white solid with a purity of 99.93% and a yield of 75%.

[0146] Example 9

[0147] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-9:

[0148]

[0149] The synthesis route of the diarylcarbazole material shown in K-9 is as follows:

[0150]

[0151] Synthesis of H-9: Add intermediate F-1 (55.1 g, 0.126 mol, 1.0 eq), 1-bromo-2-naphthylamine G-9 (29.4 g, 0.133 mol, 1.05 eq), potassium carbonate (34.8 g, 0.252 mol, 2.0 eq), 400 mL toluene and 150 mL pure water to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, add bistriphenylphosphine palladium dichloride (0.9 g, 0.0013 mol, 0.01 eq) under continuous nitrogen protection, and then heat to reflux for 3 h. HPLC monitors the complete reaction of intermediate F-1. After HPLC is qualified, cool to 50 ° C, stand to separate the water layer, wash the organic phase with 100 mL of water once, keep warm at 60 ° C and pass through a 5 cm thick silica gel column and rinse the silica gel with an appropriate amount of toluene. The organic layers were combined, toluene was evaporated at normal pressure, and then 150 mL of ethanol was added to reflux and slurry for 1 h. The temperature was lowered to 25° C. and filtered to obtain 47.3 g of an off-white solid with a purity of 98.5% and a yield of 83%.

[0152] Synthesis of I-9: Add intermediate H-9 (47.3g, 0.105mol, 1.0eq), potassium tert-butoxide (23.7g, 0.211mol, 2.0eq) and 100mL dimethyl sulfoxide to a 500mL reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, start stirring, pass nitrogen, heat the material to 90°C and keep it for 3h, and monitor the complete reaction of intermediate H-9 by HPLC. After HPLC is qualified, cool to room temperature, add 250mL water, stir for 0.5h, filter, and rinse the filter cake with water. Transfer the filter cake to a bottle, add 300mL chlorobenzene and heat to evaporate the water-soluble material, keep it at 130°C and pass it through a 5cm thick silica gel column, then concentrate to 100mL, cool to 25°C for crystallization for 1h, filter, and obtain 45.2g of off-white solid with a purity of 99.1% and a yield of 81%.

[0153] Synthesis of K-9: Into a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-9 (45.2g, 0.085mol, 1.0eq), p-bromophenylnaphthalene J-5 (26.5g, 0.093mol, 1.1eq), sodium tert-butoxide (12.2g, 0.128mol, 1.5eq) and 500mL toluene were placed, stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (7.1g, 0.0035mol, 0.04eq) and tri(benzylideneacetone)dipalladium (0.8g, 0.0009mol, 0.01eq) were added, and the temperature was raised to reflux for reaction for 2h, and sampling HPLC was taken to monitor the completion of the reaction of intermediate I-9. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the temperature was kept at 80°C, passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to evaporate toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and an off-white solid was obtained by filtration. It was then recrystallized twice from toluene / ethyl acetate to obtain 38.3 g of an off-white solid with a purity of 99.90% and a yield of 71%.

[0154] Example 10

[0155] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-10:

[0156]

[0157] The synthesis route of the diarylcarbazole material shown in K-10 is as follows:

[0158]

[0159] Synthesis of H-10: Add intermediate F-1 (55.1 g, 0.126 mol, 1.0 eq), 2-bromo-1-naphthylamine G-10 (29.4 g, 0.133 mol, 1.05 eq), potassium carbonate (34.8 g, 0.252 mol, 2.0 eq), 400 mL toluene and 150 mL pure water to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, add bistriphenylphosphine palladium dichloride (0.9 g, 0.0013 mol, 0.01 eq) under continuous nitrogen protection, and then heat to reflux for 3 h. HPLC monitors the complete reaction of intermediate F-1. After HPLC is qualified, cool to 50 ° C, stand to separate the water layer, wash the organic phase with 100 mL of water once, keep warm at 60 ° C and pass through a 5 cm thick silica gel column and rinse the silica gel with an appropriate amount of toluene. The organic layers were combined, toluene was evaporated at normal pressure, and then 150 mL of ethanol was added to reflux and slurry for 1 h. The temperature was lowered to 25° C. and filtered to obtain 45.6 g of an off-white solid with a purity of 98.6% and a yield of 80%.

[0160] Synthesis of I-10: Add intermediate H-10 (45.6 g, 0.101 mol, 1.0 eq), potassium tert-butoxide (22.7 g, 0.202 mol, 2.0 eq) and 100 mL of dimethyl sulfoxide to a 500 mL reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, start stirring, introduce nitrogen, heat the material to 90 ° C and keep the reaction for 3 hours, and monitor the complete reaction of intermediate H-10 by HPLC. After HPLC is qualified, cool to room temperature, add 250 mL of water, stir for 0.5 h, filter, and rinse the filter cake with water. Transfer the filter cake to a bottle, add 300 mL of chlorobenzene, heat and evaporate the water-soluble material, keep warm at 130 ° C and pass through a 5 cm silica gel column, then concentrate to 100 mL, cool to 25 ° C for crystallization for 1 hour, filter, and obtain 43.0 g of off-white solid with a purity of 98.7% and a yield of 80%.

[0161] Synthesis of K-10: In a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-10 (43.0 g, 0.081 mol, 1.0 eq), p-bromophenylnaphthalene J-5 (26.5 g, 0.093 mol, 1.15 eq), sodium tert-butoxide (12.2 g, 0.128 mol, 1.6 eq) and 500 mL of toluene were placed. Stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (7.0 g, 0.0032 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the temperature was raised to reflux for reaction for 2 h, and sampling was performed to monitor the complete reaction of intermediate I-10 by HPLC. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the mixture was kept at 80°C and passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to remove toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and an off-white solid was obtained by filtration. The off-white solid was recrystallized twice from toluene / ethyl acetate to obtain 37.1 g of an off-white solid with a purity of 99.93% and a yield of 72%.

[0162] Embodiment 11

[0163] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-11:

[0164]

[0165] The synthesis route of the diarylcarbazole material shown in K-11 is as follows:

[0166]

[0167] Synthesis of H-11: Add intermediate F-1 (55.1 g, 0.126 mol, 1.0 eq), 3-bromo-2-naphthylamine G-11 (29.4 g, 0.133 mol, 1.05 eq), potassium carbonate (34.8 g, 0.252 mol, 2.0 eq), 400 mL toluene and 150 mL pure water to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, add bistriphenylphosphine palladium dichloride (0.9 g, 0.0013 mol, 0.01 eq) under continuous nitrogen protection, and then heat to reflux for 3 h. HPLC monitors the complete reaction of intermediate F-1. After HPLC is qualified, cool to 50 ° C, stand to separate the water layer, wash the organic phase with 100 mL of water once, keep warm at 60 ° C and pass through a 5 cm thick silica gel column and rinse the silica gel with an appropriate amount of toluene. The organic layers were combined, toluene was evaporated at normal pressure, and then 150 mL of ethanol was added to reflux and slurry for 1 h. The temperature was lowered to 25° C. and filtered to obtain 47.3 g of an off-white solid with a purity of 98.2% and a yield of 83%.

[0168] Synthesis of I-11: Add intermediate H-11 (47.3 g, 0.105 mol, 1.0 eq), potassium tert-butoxide (23.7 g, 0.211 mol, 2.0 eq) and 100 mL of dimethyl sulfoxide to a 500 mL reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, start stirring, introduce nitrogen, heat the material to 90 ° C and keep the reaction for 3 hours, and monitor the complete reaction of intermediate H-11 by HPLC. After HPLC is qualified, cool to room temperature, add 250 mL of water, stir for 0.5 h, filter, and rinse the filter cake with water. Transfer the filter cake to a bottle, add 300 mL of chlorobenzene, heat and evaporate the water-soluble material, keep warm at 130 ° C and pass through a 5 cm silica gel column, then concentrate to 100 mL, cool to 25 ° C for crystallization for 1 hour, filter, and obtain 44.6 g of off-white solid with a purity of 98.9% and a yield of 80%.

[0169] Synthesis of K-11: Into a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-11 (44.6 g, 0.084 mol, 1.0 eq), p-bromophenylnaphthalene J-5 (26.5 g, 0.093 mol, 1.1 eq), sodium tert-butoxide (12.2 g, 0.128 mol, 1.5 eq) and 500 mL of toluene were placed, stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (7.1 g, 0.0035 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the temperature was raised to reflux for reaction for 2 h, and sampling HPLC was taken to monitor the completion of the reaction of intermediate I-11. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the temperature was kept at 80°C, passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to evaporate toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and an off-white solid was obtained by filtration. The off-white solid was recrystallized twice from toluene / ethyl acetate to obtain 37.3 g of an off-white solid with a purity of 99.91% and a yield of 70%.

[0170] Example 12

[0171] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-12:

[0172]

[0173] The synthesis route of the diarylcarbazole material shown in K-12 is as follows:

[0174]

[0175] Synthesis of H-12: Add intermediate F-1 (55.1 g, 0.126 mol, 1.0 eq), 3-phenyl-2-bromo-1-aniline G-12 (33.0 g, 0.133 mol, 1.05 eq), potassium carbonate (34.8 g, 0.252 mol, 2.0 eq), 400 mL toluene and 150 mL pure water to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, add bistriphenylphosphine palladium dichloride (0.9 g, 0.0013 mol, 0.01 eq) under continuous nitrogen protection, and then heat to reflux for 3 h. HPLC monitors the complete reaction of intermediate F-1. After HPLC is qualified, cool to 50 ° C, stand to separate the water layer, wash the organic phase with 100 mL of water once, keep warm at 60 ° C and pass through a 5 cm thick silica gel column, and rinse the silica gel with an appropriate amount of toluene. The organic layers were combined, toluene was evaporated at normal pressure, and then 150 mL of ethanol was added to reflux and slurry for 1 h. The temperature was lowered to 25° C. and filtered to obtain 42.2 g of an off-white solid with a purity of 97.5% and a yield of 70%.

[0176] Synthesis of I-12: Add intermediate H-12 (42.2 g, 0.088 mol, 1.0 eq), potassium tert-butoxide (19.8 g, 0.176 mol, 2.0 eq) and 100 mL of dimethyl sulfoxide to a 500 mL reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, start stirring, introduce nitrogen, heat the material to 90 ° C and keep the reaction for 3 h, and monitor the complete reaction of intermediate H-12 by HPLC. After HPLC is qualified, cool to room temperature, add 250 mL of water, stir for 0.5 h, filter, and rinse the filter cake with water. Transfer the filter cake to a bottle, add 300 mL of chlorobenzene, heat and evaporate the water-soluble material, keep 130 ° C and pass through a 5 cm silica gel column, then concentrate to 100 mL, cool to 25 ° C for crystallization for 1 h, filter, and obtain 31.5 g of off-white solid with a purity of 98.9% and a yield of 78%.

[0177] Synthesis of K-12: Into a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-12 (31.5 g, 0.069 mol, 1.0 eq), m-bromophenylnaphthalene J-12 (21.5 g, 0.076 mol, 1.1 eq), sodium tert-butoxide (9.9 g, 0.104 mol, 1.5 eq) and 500 mL of toluene were added, stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (5.6 g, 0.0028 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.63 g, 0.0007 mol, 0.01 eq) were added, and the temperature was raised to reflux for reaction for 2 h, and sampling HPLC was taken to monitor the completion of the reaction of intermediate I-12. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the mixture was kept at 80°C and passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to remove toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and an off-white solid was obtained by filtration. The off-white solid was recrystallized twice from toluene / ethyl acetate to obtain 31.9 g of an off-white solid with a purity of 99.92% and a yield of 70%.

[0178] Example 13

[0179] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-13:

[0180]

[0181] The synthesis route of the diarylcarbazole material shown in K-13 is as follows:

[0182]

[0183] Synthesis of H-13: Add intermediate F-1 (55.1 g, 0.126 mol, 1.0 eq), 4-phenyl-2-bromo-1-aniline G-13 (33.0 g, 0.133 mol, 1.05 eq), potassium carbonate (34.8 g, 0.252 mol, 2.0 eq), 400 mL toluene and 150 mL pure water to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, add bistriphenylphosphine palladium dichloride (0.9 g, 0.0013 mol, 0.01 eq) under continuous nitrogen protection, and then heat to reflux for 3 h. HPLC monitors the complete reaction of intermediate F-1. After HPLC is qualified, cool to 50 ° C, stand to separate the water layer, wash the organic phase with 100 mL of water once, keep warm at 60 ° C and pass through a 5 cm thick silica gel column, and rinse the silica gel with an appropriate amount of toluene. The organic layers were combined, toluene was evaporated at normal pressure, and then 150 mL of ethanol was added to reflux and slurry for 1 h. The temperature was lowered to 25° C. and filtered to obtain 50.6 g of an off-white solid with a purity of 98.5% and a yield of 84%.

[0184] Synthesis of I-13: Add intermediate H-13 (50.6 g, 0.106 mol, 1.0 eq), potassium tert-butoxide (23.9 g, 0.212 mol, 2.0 eq) and 100 mL of dimethyl sulfoxide to a 500 mL reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, start stirring, introduce nitrogen, heat the material to 90 ° C and keep the reaction for 3 h, and monitor the complete reaction of intermediate H-13 by HPLC. After HPLC is qualified, cool to room temperature, add 250 mL of water, stir for 0.5 h, filter, and rinse the filter cake with water. Transfer the filter cake to a bottle, add 300 mL of chlorobenzene, heat and evaporate the water-soluble material, keep warm at 130 ° C and pass through a 5 cm silica gel column, then concentrate to 100 mL, cool to 25 ° C for crystallization for 1 h, filter, and obtain 39.4 g of off-white solid with a purity of 98.2% and a yield of 81%.

[0185] Synthesis of K-13: Into a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-13 (39.4 g, 0.086 mol, 1.0 eq), m-bromophenylnaphthalene J-12 (26.8 g, 0.095 mol, 1.1 eq), sodium tert-butoxide (12.4 g, 0.129 mol, 1.5 eq) and 500 mL of toluene were added, stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (7.0 g, 0.0034 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the temperature was raised to reflux for reaction for 2 h, and sampling HPLC was taken to monitor the completion of the reaction of intermediate I-13. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the temperature was kept at 80°C, passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to evaporate toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and an off-white solid was obtained by filtration. The off-white solid was recrystallized twice from toluene / ethyl acetate to obtain 41.5 g of an off-white solid with a purity of 99.90% and a yield of 73%.

[0186] Embodiment 14

[0187] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-14:

[0188]

[0189] The synthesis route of the diarylcarbazole material shown in K-14 is as follows:

[0190]

[0191] Synthesis of H-14: Add intermediate F-1 (55.1 g, 0.126 mol, 1.0 eq), 5-phenyl-2-bromo-1-aniline G-14 (33.0 g, 0.133 mol, 1.05 eq), potassium carbonate (34.8 g, 0.252 mol, 2.0 eq), 400 mL toluene and 150 mL pure water to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, add bistriphenylphosphine palladium dichloride (0.9 g, 0.0013 mol, 0.01 eq) under continuous nitrogen protection, and then heat to reflux for 3 h. HPLC monitors the complete reaction of intermediate F-1. After HPLC is qualified, cool to 50 ° C, stand to separate the water layer, wash the organic phase with 100 mL of water once, keep warm at 60 ° C and pass through a 5 cm thick silica gel column, and rinse the silica gel with an appropriate amount of toluene. The organic layers were combined, toluene was evaporated at normal pressure, and then 150 mL of ethanol was added to reflux and slurry for 1 h. The temperature was lowered to 25° C. and filtered to obtain 50.5 g of an off-white solid with a purity of 98.2% and a yield of 83.9%.

[0192] Synthesis of I-14: Add intermediate H-14 (50.5 g, 0.106 mol, 1.0 eq), potassium tert-butoxide (23.9 g, 0.212 mol, 2.0 eq) and 100 mL of dimethyl sulfoxide to a 500 mL reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, start stirring, introduce nitrogen, heat the material to 90 ° C and keep the reaction for 3 h, and monitor the complete reaction of intermediate H-14 by HPLC. After HPLC is qualified, cool to room temperature, add 250 mL of water, stir for 0.5 h, filter, and rinse the filter cake with water. Transfer the filter cake to a bottle, add 300 mL of chlorobenzene, heat and evaporate the water-soluble material, keep warm at 130 ° C and pass through a 5 cm silica gel column, then concentrate to 100 mL, cool to 25 ° C for crystallization for 1 h, filter, and obtain 40.4 g of off-white solid with a purity of 98.3% and a yield of 83%.

[0193] Synthesis of K-14: Into a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-14 (40.4g, 0.088mol, 1.0eq), p-bromophenylnaphthalene J-5 (27.4g, 0.097mol, 1.1eq), sodium tert-butoxide (12.4g, 0.129mol, 1.5eq) and 500mL toluene were placed, stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (7.0g, 0.0034mol, 0.04eq) and tri(benzylideneacetone)dipalladium (0.8g, 0.0009mol, 0.01eq) were added, and the temperature was raised to reflux for reaction for 2h, and sampling HPLC was taken to monitor the completion of the reaction of intermediate I-14. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the temperature was kept at 80°C, passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to evaporate toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and filtered to obtain an off-white solid, which was then recrystallized twice from toluene / ethyl acetate to obtain 43 g of an off-white solid with a purity of 99.94% and a yield of 74%.

[0194] Embodiment 15

[0195] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-15:

[0196]

[0197] The synthesis route of the diarylcarbazole material shown in K-15 is as follows:

[0198]

[0199] Synthesis of H-15: Add intermediate F-6 (58.8 g, 0.121 mol, 1.0 eq), 1-bromo-2-naphthylamine G-9 (28.2 g, 0.127 mol, 1.05 eq), potassium carbonate (33.4 g, 0.242 mol, 2.0 eq), 400 mL toluene and 150 mL pure water to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, add bistriphenylphosphine palladium dichloride (0.9 g, 0.0013 mol, 0.01 eq) under continuous nitrogen protection, and then heat to reflux for 3 h. HPLC monitors the complete reaction of intermediate F-6. After HPLC is qualified, cool to 50 ° C, stand and separate the water layer, wash the organic phase with 100 mL of water once, keep warm at 60 ° C and pass through a 5 cm thick silica gel column, and rinse the silica gel with an appropriate amount of toluene. The organic layers were combined, toluene was evaporated at normal pressure, and then 150 mL of ethanol was added to reflux and slurry for 1 h. The temperature was lowered to 25° C. and filtered to obtain 60.8 g of an off-white solid with a purity of 98.1% and a yield of 83%.

[0200] Synthesis of I-15: Add intermediate H-15 (60.8 g, 0.101 mol, 1.0 eq), potassium tert-butoxide (22.7 g, 0.202 mol, 2.0 eq) and 100 mL of dimethyl sulfoxide to a 500 mL reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, start stirring, introduce nitrogen, heat the material to 90 ° C and keep the reaction for 3 h, and monitor the complete reaction of intermediate H-15 by HPLC. After HPLC is qualified, cool to room temperature, add 250 mL of water, stir for 0.5 h, filter, and rinse the filter cake with water. Transfer the filter cake to a bottle, add 300 mL of chlorobenzene, heat and evaporate the water-soluble material, keep warm at 130 ° C and pass through a 5 cm silica gel column, then concentrate to 100 mL, cool to 25 ° C for crystallization for 1 h, filter, and obtain 48.3 g of off-white solid with a purity of 99.2% and a yield of 81%.

[0201] Synthesis of K-15: In a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-15 (48.3 g, 0.082 mol, 1.0 eq), 3-bromophenyl dibenzofuran J-4 (29.2 g, 0.090 mol, 1.1 eq), sodium tert-butoxide (11.8 g, 0.123 mol, 1.5 eq) and 500 mL of toluene were placed. Stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (7.0 g, 0.0035 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the temperature was raised to reflux for 2 h, and the reaction of intermediate I-15 was monitored by HPLC. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the temperature was kept at 80°C and passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to evaporate toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and filtered to obtain an off-white solid, which was then recrystallized twice from toluene / ethyl acetate to obtain 41.6 g of an off-white solid with a purity of 99.93% and a yield of 70%.

[0202] Example 16

[0203] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-16:

[0204]

[0205] The synthesis route of the diarylcarbazole material shown in K-16 is as follows:

[0206]

[0207] Synthesis of H-16: Add intermediate F-6 (58.8 g, 0.121 mol, 1.0 eq), 5-phenyl-2-bromoaniline G-14 (31.5 g, 0.127 mol, 1.05 eq), potassium carbonate (33.4 g, 0.242 mol, 2.0 eq), 400 mL toluene and 150 mL pure water to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, add bistriphenylphosphine palladium dichloride (0.9 g, 0.0013 mol, 0.01 eq) under continuous nitrogen protection, and then heat to reflux for 3 h. HPLC monitors the complete reaction of intermediate F-6. After HPLC is qualified, cool to 50 ° C, stand and separate the water layer, wash the organic phase with 100 mL of water once, keep warm at 60 ° C and pass through a 5 cm thick silica gel column, and rinse the silica gel with an appropriate amount of toluene. The organic layers were combined, toluene was evaporated at normal pressure, and then 150 mL of ethanol was added to reflux and slurry for 1 h. The temperature was lowered to 25° C. and filtered to obtain 51.2 g of an off-white solid with a purity of 98.1% and a yield of 80%.

[0208] Synthesis of I-16: Add intermediate H-16 (51.2g, 0.097mol, 1.0eq), potassium tert-butoxide (22.7g, 0.202mol, 2.1eq) and 100mL dimethyl sulfoxide to a 500mL reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, start stirring, pass nitrogen, heat the material to 90°C and keep the reaction for 3h, and monitor the complete reaction of intermediate H-16 by HPLC. After HPLC is qualified, cool to room temperature, add 250mL water, stir for 0.5h, filter, and rinse the filter cake with water. Transfer the filter cake to a bottle, add 300mL chlorobenzene, heat and evaporate the water-soluble material, keep 130°C and pass through a 5cm silica gel column, then concentrate to 100mL, cool to 25°C for crystallization for 1h, filter, and obtain 41.4g of off-white solid with a purity of 98.6% and a yield of 84%.

[0209] Synthesis of K-16: Into a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-16 (41.4 g, 0.082 mol, 1.0 eq), 3-bromophenyl dibenzofuran J-4 (29.2 g, 0.090 mol, 1.1 eq), sodium tert-butoxide (11.8 g, 0.123 mol, 1.5 eq) and 500 mL toluene were placed. Stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (7.0 g, 0.0035 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the temperature was raised to reflux for 2 h, and the reaction of intermediate I-16 was monitored by HPLC. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the temperature was kept at 80°C and passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to evaporate toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and filtered to obtain an off-white solid, which was then recrystallized twice from toluene / ethyl acetate to obtain 44.3 g of an off-white solid with a purity of 99.91% and a yield of 72%.

[0210] Embodiment 17

[0211] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-17:

[0212]

[0213] The synthesis route of the diarylcarbazole material shown in K-17 is as follows:

[0214]

[0215] Synthesis of H-17: Add intermediate F-7 (60.2 g, 0.117 mol, 1.0 eq), 1-bromo-2-naphthylamine G-9 (27.3 g, 0.123 mol, 1.05 eq), potassium carbonate (32.3 g, 0.234 mol, 2.0 eq), 400 mL toluene and 150 mL pure water to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, add bistriphenylphosphine palladium dichloride (0.9 g, 0.0013 mol, 0.01 eq) under continuous nitrogen protection, and then heat to reflux for 3 h. HPLC monitors the complete reaction of intermediate F-7. After HPLC is qualified, cool to 50 ° C, stand to separate the water layer, wash the organic phase with 100 mL of water once, keep warm at 60 ° C and pass through a 5 cm thick silica gel column and rinse the silica gel with an appropriate amount of toluene. The organic layers were combined, toluene was evaporated at normal pressure, and then 150 mL of ethanol was added to reflux and slurry for 1 h. The temperature was lowered to 25° C. and filtered to obtain 48.2 g of an off-white solid with a purity of 97.6% and a yield of 78%.

[0216] Synthesis of I-17: Add intermediate H-17 (48.2g, 0.091mol, 1.0eq), potassium tert-butoxide (20.7g, 0.184mol, 2.0eq) and 100mL dimethyl sulfoxide to a 500mL reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, start stirring, introduce nitrogen, heat the material to 90°C and keep the reaction for 3h, and monitor the complete reaction of intermediate H-17 by HPLC. After HPLC is qualified, cool to room temperature, add 250mL water, stir for 0.5h, filter, and rinse the filter cake with water. Transfer the filter cake to a bottle, add 300mL chlorobenzene, heat and evaporate the water-soluble material, keep warm at 130°C and pass through a 5cm silica gel column, then concentrate to 100mL, cool to 25°C for crystallization for 1h, filter, and obtain 36.1g of off-white solid with a purity of 97.3% and a yield of 78%.

[0217] Synthesis of K-17: Into a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-17 (36.1 g, 0.071 mol, 1.0 eq), 4-bromophenyl dibenzofuran J-3 (25.2 g, 0.078 mol, 1.1 eq), sodium tert-butoxide (10.4 g, 0.108 mol, 1.5 eq) and 500 mL of toluene were placed. Stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (5.7 g, 0.003 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.66 g, 0.0007 mol, 0.01 eq) were added, and the temperature was raised to reflux for reaction for 2 h, and the reaction of intermediate I-17 was monitored by HPLC sampling. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the mixture was kept at 80°C and passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to remove toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and an off-white solid was obtained by filtration. The off-white solid was recrystallized twice from toluene / ethyl acetate to obtain 38.9 g of an off-white solid with a purity of 99.90% and a yield of 73%.

[0218] Embodiment 18

[0219] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-18:

[0220]

[0221] The synthesis route of the diarylcarbazole material shown in K-18 is as follows:

[0222]

[0223] Synthesis of H-18: Add intermediate F-7 (60.2 g, 0.117 mol, 1.0 eq), 2-bromo-1-naphthylamine G-10 (27.3 g, 0.123 mol, 1.05 eq), potassium carbonate (32.3 g, 0.234 mol, 2.0 eq), 400 mL toluene and 150 mL pure water to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, add bistriphenylphosphine palladium dichloride (0.9 g, 0.0013 mol, 0.01 eq) under continuous nitrogen protection, and then heat to reflux for 3 h. HPLC monitors the complete reaction of intermediate F-7. After HPLC is qualified, cool to 50 ° C, stand to separate the water layer, wash the organic phase with 100 mL of water once, keep warm at 60 ° C and pass through a 5 cm thick silica gel column and rinse the silica gel with an appropriate amount of toluene. The organic layers were combined, toluene was evaporated at normal pressure, and then 150 mL of ethanol was added to reflux for 1 h. The temperature was lowered to 25° C. and filtered to obtain 48.1 g of an off-white solid with a purity of 97.4% and a yield of 77.5%.

[0224] Synthesis of I-18: Add intermediate H-18 (48.1 g, 0.091 mol, 1.0 eq), potassium tert-butoxide (20.7 g, 0.184 mol, 2.0 eq) and 100 mL of dimethyl sulfoxide to a 500 mL reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, start stirring, introduce nitrogen, heat the material to 90 ° C and keep the reaction for 3 h, and monitor the complete reaction of intermediate H-18 by HPLC. After HPLC is qualified, cool to room temperature, add 250 mL of water, stir for 0.5 h, filter, and rinse the filter cake with water. Transfer the filter cake to a bottle, add 300 mL of chlorobenzene, heat and evaporate the water-soluble material, keep 130 ° C through a 5 cm silica gel column, and then concentrate to 100 mL, cool to 25 ° C for crystallization for 1 h, filter, and obtain 37.0 g of off-white solid with a purity of 97.8% and a yield of 80%.

[0225] Synthesis of K-18: In a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-18 (37.0 g, 0.073 mol, 1.0 eq), 4-bromophenyl dibenzofuran J-3 (26.0 g, 0.080 mol, 1.1 eq), sodium tert-butoxide (10.5 g, 0.110 mol, 1.5 eq) and 500 mL of toluene were placed. Stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (5.7 g, 0.003 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.66 g, 0.0007 mol, 0.01 eq) were added, and the temperature was raised to reflux for reaction for 2 h, and the reaction of intermediate I-18 was monitored by HPLC sampling. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the mixture was kept at 80°C and passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to remove toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and an off-white solid was obtained by filtration. The solid was recrystallized twice from toluene / ethyl acetate to obtain 39.5 g of an off-white solid with a purity of 99.93% and a yield of 72%.

[0226] Embodiment 19

[0227] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-19:

[0228]

[0229] The synthesis route of the diarylcarbazole material shown in K-19 is as follows:

[0230]

[0231] Synthesis of H-19: Add intermediate F-8 (59.3 g, 0.115 mol, 1.0 eq), 1-bromo-2-naphthylamine G-9 (26.9 g, 0.121 mol, 1.05 eq), potassium carbonate (31.8 g, 0.231 mol, 2.0 eq), 400 mL toluene and 150 mL pure water to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, add bistriphenylphosphine palladium dichloride (0.9 g, 0.0013 mol, 0.01 eq) under continuous nitrogen protection, and then heat to reflux for 3 h. HPLC monitors the complete reaction of intermediate F-8. After HPLC is qualified, cool to 50 ° C, stand to separate the water layer, wash the organic phase with 100 mL of water once, keep warm at 60 ° C and pass through a 5 cm thick silica gel column and rinse the silica gel with an appropriate amount of toluene. The organic layers were combined, toluene was evaporated at normal pressure, and then 150 mL of ethanol was added to reflux and slurry for 1 h. The temperature was lowered to 25° C. and filtered to obtain 49.2 g of an off-white solid with a purity of 98.3% and a yield of 81%.

[0232] Synthesis of I-19: Add intermediate H-19 (49.2g, 0.093mol, 1.0eq), potassium tert-butoxide (20.7g, 0.184mol, 2.0eq) and 100mL dimethyl sulfoxide to a 500mL reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, start stirring, introduce nitrogen, heat the material to 90°C and keep the reaction for 3h, and monitor the complete reaction of intermediate H-19 by HPLC. After HPLC is qualified, cool to room temperature, add 250mL water, stir for 0.5h, filter, and rinse the filter cake with water. Transfer the filter cake to a bottle, add 300mL chlorobenzene, heat and evaporate the water-soluble material, keep warm at 130°C and pass through a 5cm silica gel column, then concentrate to 100mL, cool to 25°C for crystallization for 1h, filter, and obtain 37.8g of off-white solid with a purity of 98.8% and a yield of 80%.

[0233] Synthesis of K-19: In a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-19 (37.8 g, 0.074 mol, 1.0 eq), 3-bromophenyl dibenzofuran J-4 (26.3 g, 0.081 mol, 1.1 eq), sodium tert-butoxide (10.4 g, 0.108 mol, 1.5 eq) and 500 mL of toluene were placed. Stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (5.9 g, 0.003 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.66 g, 0.0007 mol, 0.01 eq) were added, and the temperature was raised to reflux for reaction for 3 h, and the reaction of intermediate I-19 was monitored by HPLC sampling. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the mixture was kept at 80°C and passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to remove toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and an off-white solid was obtained by filtration. The off-white solid was recrystallized twice from toluene / ethyl acetate to obtain 39.4 g of an off-white solid with a purity of 99.92% and a yield of 71%.

[0234] Embodiment 20

[0235] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-20:

[0236]

[0237] The synthesis route of the diarylcarbazole material shown in K-20 is as follows:

[0238]

[0239] Synthesis of H-20: Add intermediate F-8 (59.3 g, 0.115 mol, 1.0 eq), 2-bromo-1-naphthylamine G-10 (26.9 g, 0.121 mol, 1.05 eq), potassium carbonate (31.8 g, 0.231 mol, 2.0 eq), 400 mL toluene and 150 mL pure water to a 1 L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser. Start stirring, add bistriphenylphosphine palladium dichloride (0.9 g, 0.0013 mol, 0.01 eq) under continuous nitrogen protection, and then heat to reflux for 3 h. HPLC monitors the complete reaction of intermediate F-8. After HPLC is qualified, cool to 50 ° C, stand and separate the water layer, wash the organic phase with 100 mL of water once, keep warm at 60 ° C and pass through a 5 cm thick silica gel column and rinse the silica gel with an appropriate amount of toluene. The organic layers were combined, toluene was evaporated at normal pressure, and then 150 mL of ethanol was added to reflux and slurry for 1 h. The temperature was lowered to 25° C. and filtered to obtain 48.1 g of an off-white solid with a purity of 97.6% and a yield of 79%.

[0240] Synthesis of I-20: Add intermediate H-20 (48.1 g, 0.091 mol, 1.0 eq), potassium tert-butoxide (20.5 g, 0.182 mol, 2.0 eq) and 100 mL of dimethyl sulfoxide to a 500 mL reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, start stirring, introduce nitrogen, heat the material to 90 ° C and keep the reaction for 3 hours, and monitor the complete reaction of intermediate H-20 by HPLC. After HPLC is qualified, cool to room temperature, add 250 mL of water, stir for 0.5 h, filter, and rinse the filter cake with water. Transfer the filter cake to a bottle, add 300 mL of chlorobenzene, heat and evaporate the water-soluble material, keep warm at 130 ° C and pass through a 5 cm silica gel column, then concentrate to 100 mL, cool to 25 ° C for crystallization for 1 hour, filter, and obtain 37.8 g of off-white solid with a purity of 98.2% and a yield of 78%.

[0241] Synthesis of K-20: In a 1L reaction bottle equipped with a stirrer, a thermometer and a reflux condenser, intermediate I-20 (36.3 g, 0.071 mol, 1.0 eq), 4-bromophenyl dibenzofuran J-3 (25.3 g, 0.078 mol, 1.1 eq), sodium tert-butoxide (10.4 g, 0.108 mol, 1.5 eq) and 500 mL of toluene were placed. Stirring was started, nitrogen was introduced, and when the material was heated to 60°C, 10% tri-tert-butylphosphine toluene solution (5.9 g, 0.003 mol, 0.04 eq) and tri(benzylideneacetone)dipalladium (0.66 g, 0.0007 mol, 0.01 eq) were added, and the temperature was raised to reflux for reaction for 3 h, and the reaction of intermediate I-20 was monitored by HPLC. After the reaction was completed, the temperature was lowered to 50°C, 100 mL of water was added to quench the reaction, the water was separated, the organic phase was washed with water again, the mixture was kept at 80°C and passed through a 5 cm silica gel column and the silica gel was eluted, the combined filtrate was concentrated to remove toluene, the temperature was lowered to 80°C, 160 mL of ethanol was added, the temperature was lowered to 25°C, and an off-white solid was obtained by filtration. The off-white solid was recrystallized twice from toluene / ethyl acetate to obtain 38.4 g of an off-white solid with a purity of 99.91% and a yield of 72%.

[0242] Comparative Example

[0243] The synthetic route of the existing method intermediate L5 is as follows:

[0244]

[0245] In a 1L reaction bottle equipped with a stirrer, a thermometer, and a reflux condenser, L4 (37.8 g, 0.09 mol, 1.0 eq), cesium carbonate (60 g, 0.18 mol, 2.0 eq), palladium acetate (0.81 g, 3.6 mmol, 0.04 eq) and 270 mL of methyl pyrrolidone NMP were placed, nitrogen was introduced under stirring, and finally 30 mL of tri-tert-butylphosphine was added. The temperature was raised to 130°C and the reaction was carried out for 3 h. The reaction of the raw material L4 was completed by HPLC monitoring, and the ratio of the main product L5 to the isomeric by-products in the reaction solution was 84%:12%. The temperature was lowered to 50°C, 450 mL of water was added, 300 mL of toluene was added for extraction and washed twice with water, the toluene organic phase was passed through a silica gel column and the silica gel was rinsed, the filtrate was combined, and concentrated under negative pressure until the material was precipitated in a thick state, the temperature was lowered to 25°C, filtered, and the filter cake was rinsed with 100 mL of ethanol, and the toluene recrystallization operation was repeated twice to obtain 21.6 g of off-white color with a purity of 99.61% and a yield of 62.7%.

[0246] Due to the presence of two ring-closing sites, isomers are generated, which reduces the main purity of the reaction. At the same time, in order to remove the isomers, it is necessary to increase the number of purification times, resulting in material waste and reduced yield. The yield of this ring-closing reaction is only 62.7%, which is much lower than the average yield of about 80% of the ring-closing reaction of the present invention.

[0247] Device Embodiment

[0248] This embodiment provides an organic electroluminescent device, such as Figure 2 As shown, it includes an anode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7 and a cathode 8 which are sequentially stacked on a substrate 1, and its device structure is: substrate + anode (indium tin oxide (ITO) coated glass substrate) / hole injection layer (HIL) / hole transport layer (HTL) / light-emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / cathode (Al).

[0249] The materials for manufacturing the organic electroluminescent device are as follows:

[0250]

[0251] Examples 1 to 20 provide diarylcarbazole materials.

[0252] The preparation of the organic electroluminescent device comprises the following steps:

[0253] 1) Substrate cleaning:

[0254] The glass substrate coated with transparent ITO is ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤10wt%, triethanolamine ≤1wt%), then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (the volume ratio of acetone to ethanol is 1:1), baked in a clean environment until the moisture is completely removed, and then cleaned with ultraviolet light and ozone.

[0255] 2) Preparation of organic layer:

[0256] Transfer the ITO transparent substrate to the evaporation equipment and evacuate to 1×10 -6 Up to 2×10 -4 Pa, 10nm hole injection layer (HIL) / 80nm hole transport layer (HTL) / 38nm light-emitting layer (EML) / 30nm electron transport layer (ETL) / 1nm electron injection layer (EIL) / 80nm thick cathode (Al) are deposited on the anode film in sequence.

[0257] in:

[0258] The material of the hole injection layer (HIL) is a mixture of NDP-9 and HT, wherein the mass ratio of NDP-9 to HT is 3:97;

[0259] The material of the hole transport layer (HTL) is HT;

[0260] The material of the light-emitting layer (EML) includes a host material and a guest material, wherein the host material is an organic electroluminescent composition formed by mixing the K1-K20 compounds prepared in Examples 1-20 with N-type in a certain proportion, and the guest material is RD-5; the specific materials and proportions are shown in Table 1;

[0261] The material of the electron transport layer (ETL) is ET-1;

[0262] The material of the electron injection layer (EIL) is LiQ; some layers of the organic electroluminescent device and their materials and thicknesses are shown in Table 1.

[0263] Table 1 Partial layers of organic electroluminescent devices and their materials and thicknesses

[0264]

[0265] Test Case

[0266] The organic electroluminescent devices obtained from device examples 1 to 20 in the device examples were tested.

[0267] Instruments: The device's current, voltage, brightness, luminous spectrum and other characteristics are tested synchronously using a PR 650 spectrum scanning luminance meter and a Keithley K 2400 digital source meter system;

[0268] Test conditions: Photoelectric properties Test conditions: Current density is 10mA / cm 2 .

[0269] Life test: current density is 50mA / cm 2 , record the time (in hours) when the device brightness drops to 95% of the original brightness.

[0270] The device performance test results are shown in Table 2:

[0271] Table 2 Device performance test results

[0272]

[0273]

[0274] As can be seen from Table 2, the host material obtained by the preparation method based on the diaryl carbazole material provided by the present invention has obtained good performance on the red light OLED device: the driving voltage is 3.30-3.58V, the current efficiency is 19.25-24.56Cd / A, and the life (T95) is 215.7-296.4hrs. Its lower driving voltage, good current efficiency and longer operating life fully reflect the structural advantages based on the diaryl carbazole material. The new preparation method provided by the present invention provides a new solution for the development and research of diaryl carbazole materials, which greatly expands the application of carbazole materials in the field of red light host materials.

[0275] The above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the present invention.

[0276] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A preparation method based on diarylcarbazole material, characterized in that: The following steps are involved: 4-bromo-2-chloro-1-fluorobenzene is used to obtain intermediate A through nitration reaction; Intermediate A and 1-naphthaleneboronic acid are used to obtain coupling intermediate B through Suzuki coupling reaction; Intermediate C is prepared by using intermediate B through nitro ring-closing reaction; The intermediate C is coupled with iodobenzene or iodobenzene derivative D to synthesize intermediate E; Intermediate E is used to prepare the boric acid pinacol ester intermediate F; Intermediate F and o-bromoaniline or o-bromoaniline derivative G are subjected to Suzuki coupling reaction to obtain intermediate H; The intermediate H is cyclized under alkaline conditions to obtain the intermediate I; The intermediate I and the halogenated aryl derivative J are coupled to obtain the diaryl carbazole material K; The synthetic route is as follows: wherein R1-R3 are independently selected from hydrogen, deuterium, halogen, cyano, C1-C30 substituted or unsubstituted alkyl, C2-C30 substituted or unsubstituted alkenyl, C2-C30 substituted or unsubstituted alkynyl, C3-C30 substituted or unsubstituted cycloalkyl, C1-C30 substituted or unsubstituted alkoxy, C1-C30 substituted or unsubstituted silanyl, C6-C60 substituted or unsubstituted aryl, C3-C30 substituted or unsubstituted heteroaryl, or Ring A that shares one side with an adjacent phenyl group to form a condensed ring; The ring A is selected from a benzene ring, a 3- to 7-membered saturated or partially unsaturated carbon ring, a 3- to 7-membered saturated or partially unsaturated hetero ring, a C6-C60 fused ring aromatic group, or a C3-C30 fused ring hetero aromatic group.

2. The method for preparing a diarylcarbazole material according to claim 1, characterized in that: The iodobenzene or iodobenzene derivative D comprises the following structure: The o-bromoaniline or o-bromoaniline derivative G comprises one of the following structures:

3. The preparation method based on diarylcarbazole material according to claim 1, characterized in that: The halogenated aryl derivative J comprises one of the following structures:

4. The method for preparing a diarylcarbazole material according to claim 1, characterized in that: The intermediate A is prepared according to the following steps: add dichloromethane, concentrated sulfuric acid and 4-bromo-2-chloro-1-fluorobenzene to the reactor in sequence, start stirring, introduce nitrogen, add 68% concentrated nitric acid dropwise at 0°C, heat to reflux for 1-2h, cool to 25±5°C, separate the lower acid solution, wash the organic phase with water, wash with sodium bicarbonate solution, wash with water and then concentrate, add n-hexane, heat to reflux for 1-2h, cool to 0±5°C, crystallize for 1-2h, filter, and dry to obtain the intermediate A; The intermediate B is prepared according to the following steps: add intermediate A, 1-naphthaleneboric acid, potassium carbonate, toluene, ethanol, and pure water into a reactor, start stirring, introduce nitrogen, add tetrakis(triphenylphosphine)palladium, heat to 75±5°C for reaction for 3-6h, cool to 35±5°C, separate the water layer and wash with water, keep at 60±5°C and pass through a silica gel column, concentrate at normal pressure, add ethanol and heat to reflux for 1-2h, cool to 25±5°C, filter, and dry to obtain intermediate B; The intermediate C is prepared according to the following steps: adding intermediate B, triphenylphosphine and o-dichlorobenzene into a reactor, starting stirring, introducing nitrogen, heating to 160±10°C for reaction for 8-12h, cooling to 90±5°C, distilling off o-dichlorobenzene under reduced pressure, cooling to 70±5°C, adding ethanol, reflux beating for 1-2h, cooling to 25±5°C, filtering, reflux beating the filter cake with n-hexane for 1-2h, cooling to 25±5°C, filtering, and drying to obtain intermediate C.

5. The method for preparing a diarylcarbazole material according to claim 1, characterized in that: The intermediate E is prepared according to the following steps: adding intermediate C, iodobenzene derivative D, cuprous iodide, 1,10-phenanthroline, potassium carbonate, and dioxane into a reactor, stirring, introducing nitrogen, heating to reflux and keeping the temperature for reaction for 8 to 12 hours, cooling to 50±5°C, filtering, rinsing the filter cake with dioxane, concentrating and evaporating to remove the dioxane, adding toluene and water to extract and separate the phases, concentrating the toluene phase at normal pressure, adding ethanol, heating to reflux and beating for 1 to 2 hours, cooling to 25±5°C, filtering, and drying to obtain the intermediate E; The intermediate F is prepared according to the following steps: adding intermediate E, pinacol borate, tri(benzylideneacetone) dipalladium, X-Phos, potassium acetate and dioxane into a reactor, starting stirring, introducing nitrogen, heating the materials to reflux reaction for 6 to 8 hours, cooling to 50±5°C, filtering, rinsing the filter cake with dioxane, concentrating and evaporating to remove dioxane, adding dichloromethane and water to extract and separate the phases, concentrating the dichloromethane phase at normal pressure, adding n-hexane, heating to reflux and beating for 1 to 2 hours, then cooling to 25±5°C, filtering, and drying to obtain intermediate F.

6. The method for preparing a diarylcarbazole material according to claim 1, characterized in that: The intermediate H is prepared according to the following steps: adding intermediate F, o-bromoaniline or o-bromoaniline derivative G, potassium carbonate, toluene and pure water into a reactor, starting stirring, adding bistriphenylphosphine palladium dichloride under nitrogen protection, heating to reflux reaction for 2 to 4 hours, cooling to 50±5°C, standing to separate the water layer, washing the organic phase with water, keeping the temperature at 60±5°C to pass through a silica gel column and eluting the silica gel, combining the organic layers, distilling toluene at normal pressure, adding ethanol to reflux and slurry for 1 to 2 hours, cooling to 25±5°C, filtering to obtain an off-white intermediate H; The intermediate I is prepared according to the following steps: adding intermediate H, potassium tert-butoxide and dimethyl sulfoxide into a reactor, starting stirring, introducing nitrogen, heating the material to 90±5°C for 2-4h of heat preservation, cooling to 25±5°C, adding water to precipitate the material, stirring for 0.5-1h, filtering, and washing the filter cake with water; transferring the filter cake to a reactor, adding chlorobenzene, heating and distilling the water-soluble material, preserving at 120±5°C to pass through a silica gel column, concentrating at normal pressure, cooling to 25±5°C, preserving for 1-2h of crystallization, filtering, and obtaining intermediate I.

7. The method for preparing a diarylcarbazole material according to claim 1, characterized in that: The diarylcarbazole material K is prepared according to the following steps: adding intermediate I, halogenated aryl derivative J, sodium tert-butoxide and toluene into a reactor, starting stirring, introducing nitrogen, and when the material temperature rises to 60±5°C, adding 10% tri-tert-butylphosphine toluene solution and tri(benzylideneacetone)dipalladium, and then heating to reflux for reaction for 1-2h, cooling to 50±5°C after the reaction, adding water to quench the reaction, separating water, washing the organic phase with water once, keeping the temperature at 80±5°C to pass through a silica gel column and eluting the silica gel, combining the filtrate, concentrating and evaporating toluene, cooling to 70±5°C, adding ethanol, cooling to 25±5°C, filtering to obtain an off-white solid, and then recrystallizing through toluene / ethyl acetate for 2-3 times to obtain an off-white solid diarylcarbazole material K.

8. The method for preparing a diarylcarbazole material according to claim 1, characterized in that: The Pd catalyst is palladium acetate, tris(dibenzylideneacetone)dipalladium, tetrakistriphenylphosphine palladium, [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium dichloromethane complex or bis(triphenylphosphine)palladium dichloride.

9. A diarylcarbazole-based material prepared by the method according to any one of claims 1 to 8.

10. Use of the diarylcarbazole-based material according to claim 9 in an organic light-emitting device.

Images